US4687715A - Zirconium pyrophosphate matrix layer for electrolyte in a fuel cell - Google Patents

Zirconium pyrophosphate matrix layer for electrolyte in a fuel cell Download PDF

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US4687715A
US4687715A US06/759,383 US75938385A US4687715A US 4687715 A US4687715 A US 4687715A US 75938385 A US75938385 A US 75938385A US 4687715 A US4687715 A US 4687715A
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matrix
matrix layer
fuel cell
electrolyte
zrp
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US06/759,383
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Norman Michael
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FUELCELL Corp OF AMERICA
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Westinghouse Electric Corp
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Assigned to WESTINGHOUSE ELECTRIC CORPORATION, WESTINGHOUSE BUILDING, GATEWAY CENTER, PITTSBURGH, PENNSYLVANIA, 15222, A CORP OF PA. reassignment WESTINGHOUSE ELECTRIC CORPORATION, WESTINGHOUSE BUILDING, GATEWAY CENTER, PITTSBURGH, PENNSYLVANIA, 15222, A CORP OF PA. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: MICHAEL, NORMAN
Priority to ZA865045A priority patent/ZA865045B/xx
Priority to JP61174695A priority patent/JPS6226764A/ja
Priority to EP86305689A priority patent/EP0216463A3/fr
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Assigned to ENVIRONMENTAL ENERGY SYSTEMS, INC. reassignment ENVIRONMENTAL ENERGY SYSTEMS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WESTINGHOUSE ELECTRIC CORPORATION
Assigned to FUELCELL CORPORATION OF AMERICA reassignment FUELCELL CORPORATION OF AMERICA CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: ENVIRONMENTAL ENERGY SYSTEMS, INC.
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • H01M8/0293—Matrices for immobilising electrolyte solutions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • This invention is concerned with fuel cells utilizing a liquid electrolyte and having an electrolyte containing matrix layer disposed between a gas diffusion anode electrode and a gas diffusion cathode electrode.
  • These fuel cells can be oriented adjacent one another and electrically connected, typically in series, to form a fuel cell stack.
  • cooling with liquid or gaseous cooling fluids is required to maintain component integrity.
  • An example of one type of fuel cell system configuration is taught by R. Kothmann et al., in U.S. Pat. No.
  • Electrodes are made from a porous graphite material with a porous graphite fiber backing, and a portion of the matrix is in the form of porous graphite saturated with phosphoric acid electrolyte. Operation of such modern phosphoric acid fuel cells is usually within a temperature range of from about 175° C. to about 225° C.
  • inorganic ion transport membranes were utilized to allow fuel cell operating temperatures of from about 75° C. to about 100° C. These membranes were about 0.03 inch thick and consisted of ZrO(H 2 PO 4 ) 2 , zirconium phosphate, i.e., zirconium orthophosphate, having active ion exchange properties, compressed under high pressure with polytetrafluoroethylene, i.e., Teflon. Each side of this inorganic ion exchange membrane was pressed to a platinum black catalyst layer and a covering platinum screen electrode.
  • Operation was characterized as: hydrogen fuel donating an electron as the hydrogen ionized at an anode electrode screen, catalyzed by the platinum black; then, hydrated by one or more molecules of water, the hydrogen ion diffused into the ion exchange membrane and was transferred across available proton sites on the PO 4 groups.
  • Such work was reported in Chemical & Engineering News (C&EN), Oct. 16, 1961 issue, at page 40.
  • inorganic ion exchange membranes by sintering a mixture containing: water balancing agent, such as aluminosilicate, aluminum sulfate, silica gel, copper sulfate, calcium chloride, and the like; water insoluble hydrous metal oxides or water insoluble acid salts, such as hydrous zirconium dioxide; and inorganic acid, such as phosphoric acid, boric acid, molybdic acid, sulfuric acid, and the like, at a temperature of from about 200° C. to 1000° C., preferably from about 300° C. to 600° C., at pressures of up to about 10,000 psi.
  • water balancing agent such as aluminosilicate, aluminum sulfate, silica gel, copper sulfate, calcium chloride, and the like
  • water insoluble hydrous metal oxides or water insoluble acid salts such as hydrous zirconium dioxide
  • inorganic acid such as phosphoric acid, boric acid, molybdic
  • This compacted, sintered, inorganic ion exchange membrane was then saturated with inorganic acid and resintered within the previously used temperature range, to provide strong bonding of the water balancing agent.
  • the resintering operation provided high transverse strength and provided a membrane capable of operational temperatures up to 125° C.
  • the examples show equal parts of ingredients, sintering at 400° C. for 5 hours and resintering at 500° C. for 2 hours, to produce an inorganic ion exchange membrane consisting essentially, of, for example, ZrO(H 2 PO 4 ) 2 with bonded aluminosilicate. If any ZrP 2 O 7 were produced, it was incidental or unnoticed, and not mentioned.
  • This ion exchange membrane was disposed between dual, platinum black catalyst-tantalum electrode screen layers.
  • the matrix component was made from oxides, sulfates or phosphates of zirconium, tantalum, tungsten, chromium or niobium, mixed with an aqueous polytetrafluorethylene dispersion, and phosphoric acid.
  • the matrix would presumably consist in major part of ZrO(H 2 PO 4 ) 2 , and unreacted ZrO, with unbound, condensed pyrophosphoric, tripolyphosphoric and tetrapolyphosphoric acids. If any ZrP 2 O 7 were produced, it was incidental or unnoticed, and not mentioned.
  • Such matrix membranes were relatively thick, had a cement consistency subject to cracking even with polytetrafluoroethylene inclusion, were reactive with phosphoric acid electrolyte, and still operated at a limiting, low temperature.
  • the layer was dried to remove water, pressed at 200 psi and sintered at 310° C. for 5 minutes, to provide a 0.04 inch thick silicon carbide-polytetrafluoroethylene matrix, essentially unreactive with phosphoric acid electrolyte and capable of operational temperatures of from about 175° C. to 200° C. While a silicon carbide matrix is well accepted, there is still need for improvement in terms of a low cost, inactive, thinner matrix material, providing high performance at higher temperatures.
  • the above needs have been met by providing a matrix layer containing particles of crystalline ZrP 2 O 7 compound with electrolyte disposed in the matrix.
  • the matrix layer will be about 93% to about 98% by weight of insulating, refractory, inactive, inert ZrP 2 O 7 particles and, an effective amount, about 2% to about 7% by weight of binder solids, preferably of fluorocarbon polymer, such as polytetrafluoroethylene (PTFE).
  • the layer will be disposed between an anode electrode and a cathode electrode of a fuel cell.
  • the ZrP 2 O 7 constituent i.e., crystalline, refractory, zirconium pyrophosphate, is non-conducting, is not an ion exchange material and has completely different physical and chemical properties than the more common active phosphates, ZrO(H 2 PO 4 ) 2 , amorphous zirconium phosphate, i.e., zirconium orthophosphate, or zirconium dioxide, i.e., ZrO 2 , and the alumino silicate, zeolite materials commonly used in ion exchange and other prior art fuel cell membranes and matrix materials.
  • essentially no ZrO(H 2 PO 4 ) or silicates, and particularly, essentially no ZrO 2 will be present in the phosphoric acid containing matrix layer of this invention since they are reactive with usual electrolytes.
  • the maximum allowable total of non-binder material reactive with acid electrolyte is about 10 wt.% of the matrix layer.
  • the maximum total of ZrO(H 2 PO 4 ) 2 plus ZrO 2 plus silicate active materials in the ready to use, sintered matrix layer is about 10 wt.% of the total weight of the matrix layer including binder solids. In all instances, the maximum amount of ZrO 2 should not be over about 5 wt.% of the total weight of the sintered matrix layer.
  • amorphous ZrO(H 2 PO 4 ) 2 .nH 2 O where n usually equals 3, is calcined at from about 1000° C. to about 1100° C., until there is no further weight loss and a completely crystalline phase, consisting of refractory ZrP 2 O 7 is produced, usually over a time period of from about 3.5 hours to about 5 hours.
  • discrete ZrP 2 O 7 particles having a particle size range of from about 2 microns to about 25 microns diameter, are mixed with a dispersion of binder solids, preferably an aqueous dispersion of polytetrafluoroethylene, in a dilute solution of a thickening agent.
  • thickening agent such as polyethylene oxide solids or the like
  • the slurry is coated onto one side of a suitable, supporting electrode substrate material by any suitable means to a thickness that will preferably provide a layer having a thickness of from about 0.002 inch to about 0.015 inch after drying and sintering.
  • the slurry is then air dried and sintered at a temperature effective to remove thickening agent and water, and to bond the electrode substrate to the matrix layer and the matrix layer components together, usually from about 200° C. to about 400° C.
  • This provides a 40% to 60% porous, relatively flexible, ultra-thin, refractory type matrix layer, substantially inactive, non-conductive and chemically resistant to hot phosphoric acid electrolyte during fuel cell operation of from about 175° C. to about 225° C.
  • a free standing matrix layer not bonded to the electrode, using substantially the same procedure, but coating onto a removable support.
  • the matrix is also crack resistant during cell operation, nonpoisoning to electrode catalyst, electronically insulating, capable of excellent acid electrolyte retention, and has good resistance to reactant gas crossover between anode and cathode.
  • a fuel cell is composed of a gas diffusion anode, a gas diffusion cathode, an an electrolyte disposed between the electrodes.
  • hydrogen is fed to the anode and oxygen is fed to the cathode.
  • oxygen is fed to the cathode.
  • the electrolyte will be contained in a porous matrix, containing one or more layers, shown as single layer 11 in the fuel cell 10 of the Drawing. Also shown are bipolar plates 12 having oxidant channels 13 and fuel channels 14.
  • the matrix layer 11, which contains phosphoric acid electrolyte is disposed between a gas diffusion cathode-catalyst layer 15 on a supporting substrate 16 and a gas diffusion anode-catalyst layer 17 on a supporting substrate 18.
  • a portion of the matrix contacting at least one electrode should be made of non-conductive material.
  • the porous matrix layer 11 of this invention comprises discrete, insulating, refractory, inert ZrP 2 O 7 particles in generally spherical form, having a particle size range of from about 2 microns to about 25 microns diameter, preferably from about 2 microns to about 10 microns, with electrolyte disposed in the matrix. Over about 25 microns, low bubble pressure will result in the matrix causing possible crossover of reacting gases. Under about 2 microns, the pore size of the matrix layer will be too small, causing a problem with wicking electrolyte into the matrix layer from an electrolyte reservoir.
  • ZrP 2 O 7 particles While these ZrP 2 O 7 particles are generally contacting; an effective amount of inert, hydrophobic hot acid resistant binder material, preferably fluorocarbon such as polytetrafluoroethylene particles or fibers preferably bind the ZrP 2 O 7 particles together, to provide good structural integrity as well as good flexibility. Phosphoric acid or other suitable electrolyte can fill the voids between the ZrP 2 O 7 particles and the polytetrafluoroethylene in the matrix.
  • fluorocarbon such as polytetrafluoroethylene particles or fibers
  • the matrix layer will generally be from about 2 mil to 15 mil thick and 40% to 60% porous.
  • the polytetrafluoroethylene materials will have a particle size range of from 0.05 micron to about 5 microns.
  • the usual viscosity of the polytetrafluoroethylene dispersion (usually 55 wt.% to 65 wt.% solids in water) is about 20 cps, at 25° C.
  • the electrolyte containing matrix layer will contain crystalline ZrP 2 O 7 .
  • the matrix in final sintered form, preferably will comprise at least about 93 wt.% ZrP 2 O 7 , most preferably about 93 wt.% to about 98 wt.% ZrP 2 O 7 , with at least about 2 wt.% binder, preferably about 2 wt.% to about 7 wt.% fluorocarbon binder.
  • the binder is effective to provide good structural integrity combined with good porosity, wicking and flexibility. Over about 7 wt.% fluorocarbon binder and its hydrophobic properties become very apparent causing wicking problems. Less than about 2 wt.% binder, structural integrity, flexibility and porosity problems result.
  • SiC insulating, inert materials, resistant to hot acid electrolyte
  • SiC insulating, inert materials, resistant to hot acid electrolyte
  • the SiC could substitute for part of the ZrP 2 O 7 , and remain in the matrix layer, without changing the useful character of the matrix layer.
  • This silicon carbide is not here considered a silicate type material.
  • a suitable thickening agent for the matrix composition slurry such as polyethylene oxide can be added. The thickening agent would be lost from the matrix during sintering. It would generally be added in very dilute aqueous solution.
  • the entire electrolyte matrix for the fuel cell will consist of a single layer, containing ZrP 2 O 7 filled with electrolyte.
  • This provides a matrix made completely from nonconducting materials. It is possible, however, to coat one of the two electrodes, preferably the cathode, with the nonconducting ZrP 2 O 7 matrix layer of this invention--to prevent shorting between electrodes--and also use another matrix layer containing carbon particles or the like filled with electrolyte in combination with the ZrP 2 O 7 layer.
  • Zirconium pyrophosphate, ZrP 2 O 7 the matrix layer material of this invention, is very different from zirconium orthophosphate ZrO(H 2 PO 4 ) 2 .
  • zirconium pyrophosphate, ZrP 2 O 7 is defined as a refractory white solid, stable to about 1550° C. and insoluble in water and dilute acids other than hydrofluoric acid. It has an almost negligible tendency to be hydrolyzed by water vapor.
  • Zirconium phosphate is defined as zirconium orthophosphate, ZrO(H 2 PO 4 ) 2 .3H 2 O, a dense white amorphous powder which is soluble in acids, derived from the action of phosphoric acid on zirconium hydroxide.
  • the crystalline, cubic form ZrP 2 O 7 used in the refractory type matrix of this invention is successfully produced as a relatively pure compound only by heating amorphous zirconium orthophosphate, ZrO(H 2 PO 4 ) 2 .nH 2 O, where n usually equals 3, at from about 1000° C. to about 1100° C. preferably for at least about 3.5 hours.
  • the ZrP 2 O 7 formed is reported to have a linear central P-O-P group, a cubic crystal structure having a unit cell edge of 8.2 Angstrom Units, Zr-O distance of 2.02 Angstrom Units, P-O distances of 1.51 and 1.56 Angstrom Units, a calculated density of 3.19 and a refractive index of 1.657 ⁇ 0.003.
  • the ZrO(H 2 PO 4 ) 2 .3H 2 O orthophosphate starting material is a non-crystalline, polymeric gel type material which is reactive, and which produces inert, crystalline ZrP 2 O 7 +5H 2 O at 1000° C.
  • the pyrophosphate can be further decomposed: 2(ZrP 2 O 7 ) going to (ZrO).sub. 2 P 2 O 7 +P 2 O 5 at 1550° C.
  • Both the ZrO(H 2 PO 4 ) 2 .3H 2 O and (ZrO) 2 P 2 O 7 would react substantially with phosphoric acid in fuel cell operation at 200° C.
  • ZrO 2 and zeolite silicates are also substantially reactive with usual fuel cell electrolyte at 200° C.
  • the ZrP 2 O 7 would not react with phosphoric acid to any substantial degree in fuel cell operations at 200° C.
  • the finished matrix including binder solids can contain no more than about 10 wt.%, preferably no more than 1 wt.% total of ZrO(H 2 PO 4 ) 2 plus ZrO 2 plus silicate active materials. Over about 5 wt.% ZrO 2 inclusion into the matrix could cause "at large" formation of a barrier type cement, in continuous large chunks, upon reaction with H 3 PO 4 at fuel cell operating temperatures, altering the discrete particle form of the matrix, and harming wicking properties. Cracking of the matrix might additionally result.
  • silicate such as zeolite alumino silicate could tend to form an amorphous material upon reaction with H 3 PO 4 at fuel cell operating temperatures, which would not function properly to provide the careful balance of properties necessary to useful matrix operation.
  • ZrO(H 2 PO 4 ) 2 .nH 2 O would tend to form growths and bridges upon reaction with H 3 PO 4 at fuel cell operating temperatures creating volume and porosity changes harmful to the matrix.
  • Over about 10 wt.% of any combination of these materials will prove harmful to the fuel cell matrix operation, with the most harmful of the three being the ZrO 2 .
  • the use of over about 5 wt.% ZrO 2 , use of over about 5 wt.% ZrO(H 2 PO 4 ) 2 .nH 2 O, use of over about 5 wt.% silicate, or use of over about 10 wt.% of the combination of these ingredients, will materially change the useful character of the matrix layer in a fundamental manner.
  • the matrix of this invention is here considered a non-active, refractory type matrix even with the inclusion of up to 7 wt.% polytetrafluoroethylene and a 10 wt.% possible inclusion of total ZrO 2 , zirconium orthophosphate and silicate.
  • Zirconium orthophosphate, ZrO(H 2 PO 4 ) 2 .3H 2 O of 99% purity was calcined at 1000° C. in a furnace.
  • X-ray diffraction analysis showed over 99% crystalline zirconium pyrophosphate, ZrP 2 O 7 after sintering at 1000° C.
  • the ZrP 2 O 7 had a particle size range of from about 2 microns to about 10 microns after calcining.
  • a coating slurry was made: 98 parts by weight of the ZrP 2 O 7 particles and 3.33 parts by weight of a 40% aqueous dispersion of polytetrafluoroethylene (2 parts by weight based on solids) having a particle size range of from 0.05 micron (sold commercially by DuPont under the tradename PTFE-30), were added to 55 parts by weight of a 99.5% aqueous solution of polyethylene oxide thickening agent (0.275 parts by weight based on solids of polyethylene oxide).
  • the ingredients were mixed to provide a thick slurry, which was then coated onto a 12 inch ⁇ 17 inch gas diffusion cathode, made of platinum coated carbon particles bonded with polytetrafluoroethylene and laminated to a wet proofed graphite paper substrate using a K-control paper nip roll coating machine made by Testing Machine Inc.
  • the coating was allowed to air dry for about 2 hours and then the coated cathode was placed in a forced air oven and the coating sintered at 330° C. for 15 minutes to remove the polyethylene oxide, and water, bond the ZrP 2 O 7 and polytetrafluoroethylene, and bond the single layered matrix to the cathode surface.
  • the matrix was a powdery film with a certain degree of flexibility, containing bound discrete particles of ZrP 2 O 7 .
  • the coated electrode was weighed.
  • the matrix coating contained 98 wt.% ZrP 2 O 7 and 2 wt.% polytetrafluoroethylene, weighed 47.5 grams, was about 50% porous and was about 0.011 inch thick, providing an inexpensive electrolyte matrix.
  • the large coated cathode was cut to 2 inch ⁇ 2 inch size.
  • the matrix coating was then impregnated with 100% phosphoric acid.
  • the matrix demonstrated good phosphoric acid electrolyte retention and good physical integrity.
  • the phosphoric acid containing ZrP 2 O 7 refractory type matrix-cathode combination was paired with a gas diffusion anode and operated in a fuel cell in an air and hydrogen feed environment at 191° C. After about 140 hours at 1 atmosphere pressure, at 200 ma./sq. cm., the IR-free voltage was 680 mV. The final reading after 2,088 hours of operation was 640 mV. at 200 ma./sq. cm.
  • the ZrP 2 O 7 matrix showed good integrity, exhibited excellent thermal stability, excellent chemical stability in hot 100% phosphoric acid, showed no interactions to poison the electrode catalyst, was electronically insulating, provided good resistance to reactant gas crossover between anode and cathode, and was extremely thin, providing an excellent space factor.
  • Zirconium orthophosphate of 99% purity (sold commercially by Magnesium Electron, Inc.) was heated at 500° C. for 4 hours. X-ray diffraction analysis of the cooled material after the heating did not show any crystalline ZrP 2 O 7 indicating an all amorphous zirconium orthophosphate structure. Such a material is found to retain ion exchange reactive sites and would be unstable in hot phosphoric acid in a fuel cell environment.

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US06/759,383 1985-07-26 1985-07-26 Zirconium pyrophosphate matrix layer for electrolyte in a fuel cell Expired - Fee Related US4687715A (en)

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Application Number Priority Date Filing Date Title
US06/759,383 US4687715A (en) 1985-07-26 1985-07-26 Zirconium pyrophosphate matrix layer for electrolyte in a fuel cell
ZA865045A ZA865045B (en) 1985-07-26 1986-07-07 Zirconium pyrophosphate matrix layer for electrolyte in a fuel cell
JP61174695A JPS6226764A (ja) 1985-07-26 1986-07-24 燃料電池
EP86305689A EP0216463A3 (fr) 1985-07-26 1986-07-24 Pile à combustible avec matrice comportant un électrolyte

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4781727A (en) * 1987-01-21 1988-11-01 Mitsubishi Denki Kabushiki Kaisha Method for gas sealing of phosphoric acid-type fuel cell
US5728489A (en) * 1996-12-12 1998-03-17 Valence Technology, Inc. Polymer electrolytes containing lithiated zeolite
WO1998052243A1 (fr) * 1997-05-14 1998-11-19 The Smart Chemical Company Limited Reacteur electrolytique, tel qu'une pile a combustible, dote d'une membrane en zeolite
WO1999044245A1 (fr) * 1998-02-24 1999-09-02 Ramot University Authority For Applied Research & Industrial Development Ltd. Matrices conductrice d'ions et leurs utilisations
US6447943B1 (en) * 2000-01-18 2002-09-10 Ramot University Authority For Applied Research & Industrial Development Ltd. Fuel cell with proton conducting membrane with a pore size less than 30 nm
US20030091883A1 (en) * 2000-01-18 2003-05-15 Emanuel Peled Fuel cell with proton conducting membrane
US20040126638A1 (en) * 2002-12-31 2004-07-01 Jong-Pyng Chen Layered proton exchange membrane and method for preparing the same
WO2005014474A2 (fr) * 2003-08-08 2005-02-17 Pemeas Gmbh Procede pour produire des pyrophosphates cristallins et utilisation de ces composes en tant que catalyseurs ou additifs pour des membranes, notamment des membranes de piles a combustible
US20050181255A1 (en) * 2004-02-18 2005-08-18 Jong-Pyng Chen Structures of the proton exchange membranes with different molecular permeabilities
US20110136045A1 (en) * 2003-03-18 2011-06-09 Trevor Wende Current collector plates of bulk-solidifying amorphous alloys
US20120211371A1 (en) * 2010-06-10 2012-08-23 The Ritsumeikan Trust Particulate matter amount detection system
WO2014130011A1 (fr) * 2013-02-19 2014-08-28 Clearedge Power, Llc. Composant de pile à combustible à acide phosphorique possédant une région imprégnée d'un polymère
US10164269B2 (en) 2016-08-23 2018-12-25 Doosan Fuel Cell America, Inc. Boron phosphate matrix layer
US10947117B2 (en) * 2016-06-27 2021-03-16 University Of Houston System Mechanically stable composite electrolyte for intermediate temperature fuel cell with improved proton conductivity and methods thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0306567A1 (fr) * 1986-08-19 1989-03-15 Japan Gore-Tex, Inc. Une matrice d'électrolyte pour pile à combustible et une méthode pour sa fabrication
JPS63187574A (ja) * 1987-01-29 1988-08-03 Japan Gore Tex Inc 燃料電池電極−マトリクス一体成形体及びその製法
JP5203596B2 (ja) * 2006-11-22 2013-06-05 関西電力株式会社 プロトン伝導体およびそれを含む燃料電池

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Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US5728489A (en) * 1996-12-12 1998-03-17 Valence Technology, Inc. Polymer electrolytes containing lithiated zeolite
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JPS6226764A (ja) 1987-02-04
EP0216463A3 (fr) 1988-08-17
EP0216463A2 (fr) 1987-04-01
ZA865045B (en) 1987-02-25

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